Electrodeposition of nickel



M'Sr- .bromine CHQQanCi-ph agent ,may ,be ,referre toa ithe-flallzylenet amine Patented Dec. 15, 1953 wmwmw flars'llafw'chemioalcompanygleyeland Olrlo,

slSaDrew ps- :1APP l N vemben7,$

% eri l-N 94W 512 Claims.

"This invention relates: electrodeposition of metalsland more specincfaillyfltoja, rocessor,- and solutions for us'eji-nf a; process, oifelectrodepositing nickel characterized in" thatzthe resulting ni'ckel electrodeposit is 'b'r ight asit cornesifrorngthe Dlatsulfate with nickelfchloride, such solutionlalso oontains arr-effectiveglamount" or eaeh l of; \two lcooperating addition agents, one of such "addition agents being a polyalkylene amine soluble in said solution to the extentiof at least 0.0001 gram per liter, andrhaving a molecular; weight fromv -.to 1800mm highemeandl'the. other or, said addition agents-being acyclic,- organic compqundsolublefin the acid nickel solution to the extentrofeat rleast 0.2 gm. per liter, and selectednfrom the group consisting of organic compounds containing the group v.0 i; L

2 shouldgbe naintamed in, the solution in; a concentration'of fron'i'oz2 to gm. per liter, prefery from 1 to 't'sm-menlite Since the two above mentioned classes of addition agents are'intrin'sically and functionally distinct, they -will' :be separately :described .and identified. The substanoesof the first addition agent class, the alkylene amines, -are-:soluble.to the extent of at least 0.0001 gm. per, liter inthe plating solution (for example in a solution containing 240 gm. per liter MSW-611203315, em;.;per liter .of NiClaGHgO, and 3715.5, gm, per -liter sBQaremainder. water) and are ezha ins; qle ula wei h IIQm- O to 1800 or higher, preferably from 600 to 1800.

The general formula; for l the unsubstituted alkylene amine compounds is as follows:

where m is an-integer from 2 -t0 4- inclusive, and n is an integer greater than=2, preferably 12-150 40. Not only unsubst itutedlalkylene. amines but also alkylene amineshaving substituents on the nitrogen, replacing hydrogen thereon maypbe. utilized within the imoleculanvweight limitations set forth above.

Examples of cqmpoundswhich may be reacted with the unsubstituted alkylene amines to replace .530 amino v hydrosen and in rease :athe molecular weight orthealkyleneamine;areas q s:

seem:

wherein s men-am nes nu ea vnsnn in i q np ii l sas r main n ..nuc1e ?b lm ca eae sa tb s a consistineso -arhy w gmethyli ethxl, chlorine,

yl. The firstvmentioned brightener and ,,'sl1 ould b intained in the plating solutiondn cgncentration from Q.0001;t to,0,1 gm. per'liter, preferably from 0.0005 to 0.05., gm.

.i w i wit twain -R si ntMatt e a t agent which I prefer to a seatta: maste "2 wes-s ews pola k len amin 10 panied by high ductility and good throwing power. The alkylene amines lower than tetraethylene pentamine are not very effective unless substituted so as to bring up the molecular weight. Numerous compounds can be used, as indicated, for increasing the molecular weight, and the substitution products are often somewhat superior to the forms of lower molecular weight. This is true even of tetraethylene pentamine, which, although a good brightener, is improved by increasing the size of the molecule.

The carriers or regulators constituting the second addition agent class are soluble in the plating solution (for example, in a solution consisting of 240 grams of NiSOr 6H2O, 37.5 grams NiC12'6H2O, 37.5 grams of 1131303, and water to make a liter) to the extent of at least 0.2 gram per liter. These include such materials as benzene and thiophene sulfonic acids and salts thereof and halogen, methyl, ethyl, CH0, and phenyl substitution products of the foregoing, such as for example:

Carriers or regulators Benzene mono-sulfonic acid (C6H5SO3H) Benzene disulfonic acids (CsH4(SOsH)2) Sodium benzene monosulfonate (CsHsSOsNa) Nickel benzene monosulfonate [(CcHsSOs) zNil Monochlor benzene monosulfonic acids (C1CcH4SOsH) Benzene monosulfonamide (C6H4SO2NH2) saccharine, sodium salt (CsH4SO2CONNa) Dichloro benzene disulfonlc acids (C12C6H2(SO3H) a) 9. 2,5-dibromo benzene sulfonic acid (BrzCsHaSOaH) 10. Toluene sulfonic acids (CHJCGHASOIiH) 11. Benzaldehyde sulfonic acids (Cal-I4 (CI-IO) SOsH) 12. Diphenyl sulfonic acids (CeHCcH4SO3I-I) 13. Benzene sulfonyl chloride (CsH5SO2C1) 14. Para chloro benzene sulfonamide 15. Xylene sulfonarnides ((CHa) zCtHsSOzNI-Iz) 16. Para toluene sulfonamide (CI-I3CsH4SO2NI-I2) 17. Thiophene sulfonic acids (C4HaS.SO:I-I)

18. Diphenyl sulfone (C6H5SO2C6H5) I 19. Naphthalene-1,5-disulphonic acid 20. Sulfonated naphthalene. (Mixtures of naphthalene sulfonic acids, produced by treating naphthalene with oleum, preferably 2 parts of 20% oleum on one part of naphthalene at 160 C. for two hours) 21. Alpha naphthalene monosulfonic acid 22. Beta naphthalene mono sulfonic acid 23. O-toluene sulfonamide 24. Chloro naphthalene disulfonates Potassium and cobalt salts are useable as well as the sodium and nickel salts indicated above.

From these examples it becomes clear that numerous single ring compounds containing the effective group can be used, whether aromatic,

such as the benzene sulfonic acids or heterocyclic with aromatic characteristics, such as thiophene sulfonic acid. Various substituents on the ring structure are exemplified.

It is to be understood that all statements made herein concerning the capabilities of the addition agents presuppose the use of one or a mixture of two or more from each class. The carrying agents produce a degree of brightness without any brightener but not enough to be satisfactory alone. I prefer the use of the more common and readily available compounds, and prefer to employ in each addition agent class only compounds devoid of the group which characterizes the other addition agent class.

The constituents of the bath according to the preferred practice of the invention are (1) water, (2) nickel sulfate, nickel chloride or nickel sulfate with nickel chloride, (3) an aromatic sulfonyl compound such as an aromatic sulfonic acid or a nickel, alkali metal, or cobalt salt thereof, an aromatic sulfonamide, or sulfimide, or a mixture of a plurality thereof, (4) a wettin agent, and (5) a polyalkylene amine or a mixture of polyalkylene amines. An additional ingredient of the solution which is desirable is a buffering agent such as boric acid, formic acid, ammonium sulfate, or the like.

It will be noted that in respect to major constituents, the solutions are similar to the well known all sulfate, all chloride, and sulfatechloride or Watts type nickel plating solutions. It will be noted also that as to the aromatic sulfonyl type of addition agent or carrier as it is often called, the group of suitable materials are of the type which is represented by well known carriers in the bright nickel plating industry. The essential novel feature of the present invention is the use in such solutions of a small amount of a polyalkylene amine or a mixture of polyalkylene amines of molecular weight from about 100 to about 1800 or even higher.

The preferred basic solutions in connection with which my invention is realized are as folows:

All sulfate All chloride NlClz.6HzO 50 to 250 gms., preferably 100 to 200 gms.

Boric acid 0 to 00 gms., preferably 10 to gins.

Wetting agent (e. g. 0 to 5 gms., preferably 0.5 to 1.0 gm.

dium lauryl sulfate).

H20 to make 1000 cc.

Sulfate-chloride (Watts type) NlSO4.7H2O-. 100 to 400 gms., preferably 200 to 300 gms.

10101151110" 10 to gms., preferably 25 to 40 gms.

Boric acid 0 to 50 gms., preferably 15 to 40 gms.

Wetting agent (e. g. so- 0.5 to 0 gm, preferably 0.05 to 0.15 gm.

dium lauryl sulfate).

To each of the foregoing basic solutions I add a suitable quantity of each, or a mixture of two or more of each, of the two cooperating addition agents. One of said addition agents or mixtures is one of the aromatic sulfonyl type and the other is of the alkylene amine type described above. The solution should, for best results, contain an anti-pit agent although the deposits may be suitable for some purposes without eliminating the pitting and, under some conditions, the deposits may not be objectionably pitted even in the absence of an addition agent for control of pitting. Sodium lauryl sulfate may be used as an antipit agent, although, as stated, its use is not essential and other wetting agents or mixtures of getting agents may be used for control of pit- The following specific examples will serve t illustrate the invention;

deposition of bright nickel, and, xwhile -'I have Nickel- Sulfate .6HzO Nickel Chloride .7H2On Boric Acid -1 Sodium Lauryl Sulfate letraethylene Pentamine Con d "with the following in the=MolecularRatiolndieated:

Acrylonitrile (1:7) MethylSulfate (1 :l2)

Epichlorohydrin (1:2) Epichlorohydrin and Phenol (1: Benzene Sulfonyl Chloride (1:2) Ohloroacetic' Acid and-"Methyl: fate 1:2: Dimethyl Chloracetal (1:2)... Tetra'ethylene' Pentamine (Monomer) IEolymerized 'letraethylene -Pentamine "of Molecular-Weight 1200 *Polymerized TctraethylenePentamlne of Molecular Weight1800- 'SuHlfonated Naphthalene 1 Sulf'onatednaphthalene is a comioeition-such'as maybe-'producd' hy reacting 2 parts of 29% oleum on one part ofnap tha=lene;:at-160 the resulting mixture with nickel carbonate, filtering a C. ion two honrwneutrulizing nd diluting to 26? B. Where quantities of sulfonuted naphthalene are referred to herein "it-is to"'beunderstood that thequantityspecifiedrepresentsi-oughly the nicke1-naphthalene-mixed sulfonate content of the mixture.

,TABLE III Bolution No l 2 1'3 4 5 6 7 i 8 Niekel Sulfate .6H2O Nickel Chloride .7H2O. -37, 5 37. 5 V Boric Aeid '37."5 "37:5 Ammonium Sulfate. 22. 5, Formic Acid Citric'Acid 'Fmmalin a Sodium Lauryl Sulfat 1 1 "letraethylene Pentamine' Condensed with Acrylonitrilein Molecular Ratio of 1:7. B-Naphthalene Monosulfonate (Ni). I a-Ghloronaphthalene Monosulionate' (Ni) a-Chloronaphthalene Disulfonate (Ni) Sulionated Naphthalene 1 "Saccharin *D v e%perature (Degrees Fahrenheit) 7 I Sulfonated'naphthalene isa composition shch as' maybe-produced by reacting? parts oleum on one part of naphthalene at 160? G: for two hoursmeutralizing the resulting mixturewith nlckel carbonate, filtering and diluting to 26 B6. -Whete quantities of fsulfonated-naphthalene are referred wherein, it is to be understood that thequ'antity specxfied rcpreserits roughly the nickel-naphthaleneinixed-sulfonateconte'nt of the mixture.

From the foregoing it will *be obY-io'us that I have provided an in'iprove'd' process for electroclaim is:

1. A method for electrodepo'siting 'nickel in -the ''-form of a deposihwhich bright as-taken-from produced by reacting awofialk'ylene" amine -bf -"said general "f0inrwithailnaterlal" of-*the class consisting ofiepichiorhydrinfacrylonitrilefmethyl sulfate, 'chloracetic acid, fepichlorhydrin with phenol, dimethyl "chloracetal, benzene --su1fony1 chloride, styreneokitiersoluhle in said solution to the extent ()f-iitleast- OI-0001: gram- 'per 'liter, and havin'g'-a molecular-weight from 100 to "1800, and the :other of xsad'cl addition agents being anorganic-compound 'of the'class consisting or benzene monosulfoni acid heriz'e'ne disulfo'nlc acids, 4 monochlor itbenzene mon'osulfonic the plating solution without 'further treatment' acids, benzene monosulfonamide, saccharine, di-

and which comprises electrolyzingan aqueous, acid solution'of' anickel'electrolyteof the class consisting of nickel :sulfate, nickel chloride; and

chloro benzenedisulfonio acids,.2,5l-dibromo benzene sulfonid'acid, toluene sulfonidacids, benzal- ,dehyde sulfonic: acids, idiphenyl :sulfonic :acids,

mixtures of nickel sulfate with nickel; chloride, benzene l l;i morida para chlorot @said solution also containing-cooperating addition agents "capable of impartinghrightness to -the deposit, one of :said' addition agents being-i; a

polyalkyleneamine'of the class 'consistin'gaof; un-

substituted amines of .thegeneral form I-I2N[(CHDmNI-I]"(GHQ1;J. TI-I2 .where m is an 7 integenfrom'fgi to 1: inclusive. and 2 n1 is'an integer greater-than;2,;iandi olyalkylene sulfon'ic uacid, beta sulfonamide,"r xyleneesulfonamides; :para stoluene :11 vsulfonamide, thiophene. sulfonic acids, ,diphenyl f s'ulfone, :naphthalene:1,5:disulphonic sacid, :sulfonated naphthalene "alphaanaphthalene monolirl'ltl'ialene wmonosulfonic acid, o-toluene sulfonamidefichloro naphthalene disulfonates and the sodium, potassium, nickel, and cobalt" salts" thereof, eaidfllrst -mentioned addition agent "-'being;fpresent in concentration amines which i are the l: condensation products iIrOmOIODO diigrannpefliten and said"second 7 mentioned addition agent being present in concentration from 0.2 to grams per'liter.

2. A method for electrodepositing nickel in the form of a deposit which is bright as taken from the plating solution without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness to the deposit, one of said addition agents being a polyalkylene amine of the class consisting of unsubstituted amines of the general form where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, and polyalkylene amines which are the condensation products produced by reacting a polyalkylene amine of said general form with a material of the class consisting of epichlorhydrin, acrylonitrile, methyl sulfate, chloracetic acid, epichlorhydrin with phenol, dimethyl chloracetal, benzene sulfonyl chloride, and styrene oxide soluble in said solution to the extent of at least 0.0005 gram per liter, and having a molecular weight from 600 to 1800, and the other of said addition agents being an organic compound of the class consisting of benzene mon-sulfonic acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphthalene-1,5-disu1phonic acid, sulfonated naphthalene, alpha naphthalene monosulfonic acid, beta naphthalene mono sulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel, and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.0005 to 0.05 gram per liter, and said second mentioned agent being present in concentration from 0.2 to 15 grams per liter.

3. A method forelectrodepositing nickel in the form of a deposit which is bright as taken from the plating solution without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and

mixtures of nickel sulfate with nickel chloride,

said solution also containing cooperating addition agents capable of imparting brightness to the deposit, one of said addition agents being an unsubstituted polyalkylene amine composition of the general form where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, of molecular weight from 100 to 1800, and the other of said addition agents being an organic compound of the class consisting of benzene monosulfonic acid, benzene disulfonic acids, monochlor benzene phenyl 'su'lfone, naphthalene 1,5 disulphonic acid; sulfonated naphthalene, alpha naphthalene monosulfonic acid, beta naphthalene mono sulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel, and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.0001 to 0.1 gram per liter, and said second mentioned addition agent being present in concentration from 0.2 to 15 grams per liter.

4. A method for electrodepositing nickel in the form of a deposit which is bright as taken from the plating solution without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness to the deposit, one of said addition agents being an unsubstituted polyalkylene amine composition of the general form where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, of molecular weight from 600 to 1800, and the other of said addition agents being an organic compound of the class consisting of benzene mono-sulfonic acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro monosulfonic acids, benzene monosulfonamide,

saccharine, dichloro benzene disulfonic acids, 25- dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, di-

benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphthalene 1,5 disulphonic acid, sulfonated naphthalene, alpha naphthalene monosulfonic acid, beta naphthalene mono sulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel, and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.0005 to 0.05 gram per liter, and said second mentioned agent being present in concentration from 0.2 to 15 grams per liter.

5. A method for electrodepositing nickel in the form of a deposit which is bright as taken from the plating solution without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness to the deposit, one of said addition agents being a condensation product of a polyalkylene amine of the general form where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, with acrylonitrile, and the other of said addition agents being an organic compound of the class consisting of benzene mono-sulfonic acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphth'aIenc- 1;5disulphenic aeid,e sulionated 'naphi: tl'mlene;- alphanaphthalene monosuitonicacid beta: naphthalene mono sulfonic aeidi o-toluene sulfdnam-iderchloronaphthalene disulto'natesand the -"sodium;- potassium; nickel; and cobaltsaits' and which comprises -elctrolyzing-an aqueous, acid-"solutionofa nickei electrolyte or the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel-" 'sulfate with nickei chloride, said =solution -also containingcooperating addi tion -agents capable of imparting-brightness to the deposit; one of-ysaid"addition-agents being' -a condensationproduct of a polyalkylene amine'bf the genera-l "form where :mris ancintegerifrom 2 f to '4-sinclusive and n a-is' an integer greater v-than2, with acrylonitril'e, and-the other ofsaid eaddition eagents beinganorganic compound of the class consistingofbenzene monosulfonic acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine; dichloro benzene disulfon-ic acids; 2,5-dib'romo' benzene sulfonic acid; toluene sulfonic acids, benzaldehyde' sul ionic acids; diphenyl"sulionic-acids;-benzene sulfo'nyl chloride; 1 para chloro benzene -sulfonamide,- xylene sulfonamides; para toluene -sulfonamide; thiophene sulfonic acids; diphenylsuifoneynaphth'alene-lfi disulfonicacid; sulfonatednaphthalene, alpha naphthalene-monosulfonic acid," beta naphthalene mono-sulfonic acid, o-toluene sulfonamide;-chloro naphthalene disulfonates and the sodium,- potassium;- nickel and? cobalt salts thereon-said first mentioned additionagent being present in concentrationfrom--0.0005-to 0.05gram perliter, and saidsecond nienti'onedagent being present inconcentration from 02 to---i grams lite1.-

7;" A -method" for electrodepositing nickel in the form of a deposit which-is bright as taken from the r-plating solution without further treatment andi which comprises electrolyzing an aqueous; acid solution of a nickel electrolyte -of 'th'e jclass consisting of nickel sulfate, nickel chloride; and mixtures ofnickel -su1fate with nickel chloride, said solution also containing, cooperating, addition agents *capable "of imparting brightness to the deposit; oneiof-isaidiadditiorn agents being a condensation product of a,po1yalkylene amine ,of the general ,form

HzN-E (CIh)'mNHi] 1i(CH2'),i'nNH2 where m is an integenfrom 2 ,,to.,4 inclusive and n is an integer greater than'*2; with epichlorinrdrimv andothe ;;-othenr of saidaddition agents being an organic compound of the class consisting of benzene monosulfonic acid, benzene disulfonic acids, monochlor benzene mono-sulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulnaphbhflienew alphas naphthalene acids beta naphthaiene momm sulfonica acid, o-tolnenesultanamideach1oiwna ahthalenesdisrlh tdnateswandithe-asodimna potassium,-=.nickehiand cobal-t' sal-ts theme; said fi'rst-i-mentionedeaddi'i 8; Ainethod for;electrodpositingtnickeuimthaform ofa -deposit which isrbright as takenafrom' the plating solution --without further- -=treatmenv and which -comprisea electvolyzinga anaaqueousracid 'solutionof a niclrel' 'elctrolyte'iof'cthe consisting ot nickel' sulfate nickekchloridee and mixtures or mickel Zsuli'ate with' nickel chiorider said solution aiso containing gcooperating addts tion agentscapable oi imparting brightness eta the dposit; one otsaid additiom. agents; being-y a condensation product of a polyalkylenecaminei' n-=is*an -integer --greaterthan 2, with epichlorhy drin;-- and-the otherot said addition-agentslbeingv an=-organic corn-pound of the class consistingaot present in concentration from 0.2 to. 15?;gran1s per litera- A method for relectrodepositin'g nickelin'the form of 'a deposit which-4s bright *as taken fromthe-p1atin-g-so1ution without further treatment and whichcomprises electrolyzing an aqueous; acid solution of a-nickel electrol-yte of the classconsist-ingfof nickelsulfate; nickel' chloride; and mixtures-of nickel sulfatewith nickel-"chloride; said 'solution alsog-containin ijcooperating qaddig tion' agents capable 01 imparting brightness; to

the -deposit, one of said addition} agents being 1 a condensation product of a polyalkylene-amine the nemil ornn HzNE (cm). armament) nds'scn nteee lrilgreatentnaraz teuandthe-nthc anl rzanic compplmd-i he p fifii 1: enzene manesul n a cid, 'esliees acids, monochlor benzene monosulfonic acids;- benzene monosuli'onamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaidehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chlorocvbenzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphthalene-1,5-disulfonic acid, sulfonated naphfone, naphthalene-1,5-disulfonig acid, sulfonated thalene, alpha n p h l n m n lfon a id.

beta naphthalene monosulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.0001 to 0.1 gram per liter, and said second mentioned addition agent being present in concentration from 0.2 to grams per liter.

10. A method for electrodepositing nickel in the form of a deposit which is bright as taken from the plating solution Without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness to the deposit, one of said addition agents being a condensation product of a polyalkylene amine of the general form where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, with methyl sulfate, and the other of said addition agents being an organic compound of the class consisting of benzene monosulfonic acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphthalene-1,5-disulfonic acid, sulfonated naphthalene, alpha naphthalene monosulfonic acid, beta naphthalene monosulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.0005 to 0.05 gram per liter, and said second mentioned agent being present in concentration from 0.2 to 15 grams per liter.

11. A method for electrodepositing nickel in the form of a deposit which is bright as taken from the plating solution without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addi tion agents capable of imparting brightness to the deposit, one of said addition agents being a condensation product of a polyalkylene amine of the general form HZNE (CH2) mNH]n(CH2) mNH2 where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, with styrene oxide,

and the other of said addition agents being an organic compound of the class consisting of henzene monosulfonie acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulionic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sultonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphthalene-1,5-disulphonic acid, sulfonated naphthalene, alpha naphthalene monosulfonic acid, beta naphthalene monosulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel, and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.001 to 0.1 gram per liter, and said second mentioned addition agent being present in concentration from 0.2 t 15 grams per liter.

12. A method for electrodepositing nickel in the form of a deposit which is bright as taken from the plating solution without further treatment and which comprises electrolyzing an aqueous, acid solution of a nickel electrolyte of the class consisting of nickel sulfate, nickel chloride, and mixtures of nickel sulfate with nickel chloride, said solution also containing cooperating addition agents capable of imparting brightness to the deposit, one of said addition agents being a condensation product of a polyalkylene amine of the general form HzNE (CH2) mNH] 1: (CH2) 1nNH2 where m is an integer from 2 to 4 inclusive and n is an integer greater than 2, with styrene oxide, and the other of said addition agents being an organic compound of the class consisting of benzene monosulfonic acid, benzene disulfonic acids, monochlor benzene monosulfonic acids, benzene monosulfonamide, saccharine, dichloro benzene disulfonic acids, 2,5-dibromo benzene sulfonic acid, toluene sulfonic acids, benzaldehyde sulfonic acids, diphenyl sulfonic acids, benzene sulfonyl chloride, para chloro benzene sulfonamide, xylene sulfonamides, para toluene sulfonamide, thiophene sulfonic acids, diphenyl sulfone, naphthalene-1,5-disulfonic acid, sulfonated naphthalene, alpha naphthalene monosulfonic acid, beta naphthalene monosulfonic acid, o-toluene sulfonamide, chloro naphthalene disulfonates and the sodium, potassium, nickel and cobalt salts thereof, said first mentioned addition agent being present in concentration from 0.0005 to 0.05 gram per liter, and said second mentioned agent being present in concentration from 0.2 to 15 grams per liter.

DAVID G. ELLIS.

References Cited in the file of this patent UNITED STATES PATENTS OTHER REFERENCES Raub et al., Metal Finishing, June 1940, pp. 315-316. 

1. A METHOD FOR ELECTRODEPOSITING NICKEL IN THE FORM OF A DEPOSIT WHICH IS BRIGHT AS TAKEN FROM THE PLATING SOLUTION WITHOUT FURTHER TREATMENT AND WHICH COMPRISES ELECTROLYZING AN AQUEOUS ACID SOLUTION OF A NICKEL ELECTROLYTE OF THE CLASS CONSISTING OF NICKEL SULFATE, NICKEL CHLORIDE, AND MIXTURES OF NICKEL SULFATE WITH NICKEL CHLORIDE, SAID SOLUTION ALSO CONTAINING COOPERATING ADDITION AGENTS CAPABLE OF IMPARTING BRIGHTNESS TO THE DEPOSIT, ONE OF SAID ADDITION AGENTS BEING A POLYALKYLENE AMINE OF THE CLASS CONSISTING OF UNSUBSTITUTED AMINES OF THE GENERAL FORM 